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Better RAFT Control is Better? Insights into the Preparation of Monodisperse Surface-Functional Polymeric Microspheres by Photoinitiated RAFT Dispersion Polymerization

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    Better RAFT Control is Better? Insights into the Preparation of Monodisperse Surface-Functional Polymeric Microspheres by Photoinitiated RAFT Dispersion Polymerization
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    • Liangliang Yu
      Liangliang Yu
      Department of Polymeric Materials and Engineering, School of Materials and Energy, Guangdong University of Technology, Guangzhou 510006, China
      More by Liangliang Yu
    • Xiaocong Dai
      Xiaocong Dai
      Department of Polymeric Materials and Engineering, School of Materials and Energy, Guangdong University of Technology, Guangzhou 510006, China
      More by Xiaocong Dai
    • Yuxuan Zhang
      Yuxuan Zhang
      Department of Polymeric Materials and Engineering, School of Materials and Energy, Guangdong University of Technology, Guangzhou 510006, China
      More by Yuxuan Zhang
    • Zhaohua Zeng
      Zhaohua Zeng
      School of Materials Science and Engineering, Sun Yat-sen University, Guangzhou 510275, China
      More by Zhaohua Zeng
    • Li Zhang
      Li Zhang
      Department of Polymeric Materials and Engineering, School of Materials and Energy, Guangdong University of Technology, Guangzhou 510006, China
      Guangdong Provincial Key Laboratory of Functional Soft Condensed Matter, Guangzhou 510006, China
      More by Li Zhang
    • Jianbo Tan*
      Jianbo Tan
      Department of Polymeric Materials and Engineering, School of Materials and Energy, Guangdong University of Technology, Guangzhou 510006, China
      Guangdong Provincial Key Laboratory of Functional Soft Condensed Matter, Guangzhou 510006, China
      *E-mail: [email protected]
      More by Jianbo Tan
      Orcidhttp://orcid.org/0000-0002-5635-7178
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    Macromolecules

    Cite this: Macromolecules 2019, 52, 19, 7267–7277
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    https://doi.org/10.1021/acs.macromol.9b01295
    Published September 19, 2019
    Copyright © 2019 American Chemical Society
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    Abstract

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    Efficient synthesis of polymeric microspheres with high uniformity, well-defined surface functionality, and precise diameter and composition has long been a challenging goal in polymer science. Herein, we exploited photoinitiated reversible addition–fragmentation transfer (RAFT) dispersion polymerization of methyl methacrylate using poly(glycerol monomethacrylate)-based macromolecular chain transfer agents (macro-CTAs). We showed that the use of a binary mixture of macro-CTA and CTA with poor controllability was crucial for obtaining monodisperse poly(methyl methacrylate) (PMMA) microspheres. Evolution of PMMA microspheres during the polymerization was followed by scanning electron microscopy and 1H NMR spectroscopy, confirming a linear evolution of particle volume with monomer conversion. PMMA microspheres with better colloidal stability were obtained when increasing the amount of macro-CTA used in photoinitiated RAFT dispersion polymerization. Finally, a two-stage photoinitiated RAFT dispersion polymerization was also explored by adding additional monomers in the second stage. We demonstrated that the particle size of polymeric microspheres could be precisely controlled by adding different amounts of the monomer in the second stage. Moreover, polymeric microspheres composed of two polymers were also prepared by adding a different monomer in the second stage. This study not only optimizes reaction conditions for preparing monodisperse surface-functional polymeric microspheres but also provides mechanistic insights into photoinitiated RAFT dispersion polymerization.

    Copyright © 2019 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.macromol.9b01295.

    • Full experimental detail, additional results, evolution of conversion with photoinitiator concentration, GPC traces of PMMA particles, RI and UV (measured at 310 nm) GPC traces of PMMA particles, SEM images of PMMA microspheres, SEM images of PMMA microspheres (1st stage) and PMMA/PBzMA microspheres (2nd stage), and TEM image of EDA-functionalized PMMA/PGlyMA microspheres (PDF)

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    Cited By

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    This article is cited by 33 publications.

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    Macromolecules

    Cite this: Macromolecules 2019, 52, 19, 7267–7277
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.macromol.9b01295
    Published September 19, 2019
    Copyright © 2019 American Chemical Society
    Request reuse permissions

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